Orthoalkylphenol-sulfur dichloride reaction products



United States Patent Ofiice 3,129,213 Patented Apr. 14, 1964 3,129,213ORTHOALKYLPHENOL-SULFUR DICHLORIDE REAOTION PRODUCTS Calvin ll. Worrel,Detroit, Mich, assignor to Ethyl Corporation, New York, N.Y., acorporation of Virginia No Drawing. Fiied Dec. 22, 1%}, Ser. No. 161,35711 Ciaims. (Cl. 260-137) This invention relates to new compositions ofmatter, more particularly to new sulfur and chlorine-containing reactionproducts.

Some phenolic compounds have found utility as antioxidants in variousorganic media. The ability of such compounds to act as antioxidants isdependent on a delicate balance of properities such as molecular weight,solubility, steric hindrance of the hydroxyl group and others which haveyet to be defined.

Certain sulfur and chlorine-containing compounds have found utility asanti-wear and extreme pressure agents. Effectiveness as such is due inpart to the aflinity of such compounds for metal surfaces. Bearings incontact with an oil containing such compounds are protected from wear bythe coating action of the additive. The anti-wear agent coats thebearing to remove it physically from the oil.

Thus the mechanisms by which the two types of additives function can becontrasted. On the one hand, antioxidants function by intimatelyco-acting with the medium, for example oil, to react with oxygen andperioxides, thus stabilizing the oil. On the other hand, anti-wearagents are more effective where their affinity for metal surfaces isgreater than their affinity for oil. They act not chemically as toantioxidants with oxygen and perom'des but rather act physically onmetal surfaces or bearings in the oil. Attempts have been made in thepast to find antioxidants which will also act as anti-wear agents. Sucha task is made difficult by the fact that the respective functions areaccomplished by contrasting mechanisms. In order to accomplish such atask a delicate balance must be achieved whereas the solubility,molecular weight, configuration, affinity and other properties of thecompounds must be such as to allow the compound to function in bothcapacities. This is not an easy task. Previous attempts have resulted incompounds which are not effective in either capacity.

It is an object of this invention to provide new compositions of matter.A further object is to provide highly effective sulfur andchlorine-containing phenolic reaction products. Another object is toprovide a new process for preparing these sulfur and chlorine-containingreaction products. Still another object is to provide new compositionsof matter which comprise various organic media, particularly mineraloils, containing the sulfur and chlorine-containing reaction products ofthis invention. Other objects of this invention will be apparent fromthe ensuing description.

Applicant has discovered a certain class of sulfur andchlorine-containing phenolic material which, contrary to the propertiesof either phenolic or sulfur and chlorinecontaining material, are notonly excellent and highly effective antioxidants in a large and variedrange of organic media but also act effectively as anti-wear and extremepressure agents for liquid organic media when such media are in contactwith a metal surface.

Further, this dual role is accomplished without resort to the use ofmetal salts. This is very significant. The use of metal-containingadditives in lubricating oil results in a buildup of metallic depositsin various parts of the engine. As a result additional additives have tobe resorted to in order to aid removal of these metallic deposits, manytimes unsuccessfully. Applicants invention in its lubricating oilembodiment avoids the necessity of such additional additives since nometallic ash is formed upon its burning.

The fact that the products of this invention act not only asantioxidants but also as highly effective anti-wear and extreme pressureagents is completely unexpected from the nature of the reactants.Anti-wear and extreme pressure agents act by coating the metal surfaceor bearing in the oil. However, these agents protect not only bypresenting a shield against chemical reaction but also by their physicalpresence, preventing contact of the metal surface with abrasiveparticles in the oil. These abrasive particles can be metallic in natureor they can be reaction or deterioration products of the oil.

Further, applicants products have excellent oil solubility. Solubilityis extremely important to the usefulness of a product as an oiladditive. Products which have only limited solubility in oil tend todeposit out when the oil is subjected to extermes of temperatures andpressure. This handicap is usually associated with products containingsulfur or chlorine. Applicants products, however, have excellent oilsolubility and do not form deposits when the oil is subjected to harshtreatment.

Thus applicants products possess two outstanding advantages. They areantioxidants and anti-wear and extreme pressure agents combined and aremost superior in each capacity.

In accordance with the present invention new compositions of matter areprovided which consist of the sulfur and chlorine-containing phenolicproduct obtained by reaction between (1) a phenolic compound having,ortho to the phenolic hydroxyl group, an alkyl group of from 3-8 carbonatoms and (2) sulfur dichloride; there being at least about 1.0 mole ofsaid sulfur dichloride per mole of phenol as reactants.

The sulfur and chlorine-containing phenolic products of this inventionare substantially involatile, oil soluble, clear, reddish-yellow,viscous semi-solids or resins. These products are complex in chemicalstructure. When subjected to elemental chemical analyses they do notcorrespond to any specific chemical formula. To further characterize theproduct, infrared as well as visible and ultraviolet spectra techniqueswere attempted. However, they afiorded little help. Characteristic bandsfor sulfur-phenol and chlorine-phenol bonds are weak at best.

Elemental analysis, however, does afford a means for furthercharacterizing the products of this invention. Thus applicants inventioncan be defined in terms of its carbon, hydrogen, sulfur and chlorinecontent as well as its average molecular weight. Thus, the products ofthis invention can be described as antioxidant material con taining 50to 62 percent carbon, 4.5 to 7.2 percent hydrogen, 34 to 11 percentsulfur, and having a molecular weight of from 500 to 740.

Accordingly, an embodiment of this invention is a substantiallyinvolatile, reddish-yellow polynuclear phenolic compound containing 2 to5 phenolic nuclei wherein each phenolic nuclei contains one hydroxylradical and one alkyl group of 3-8 carbon atoms ortho to said hydroxylradical, said phenolic nuclei being linked together in a straight chain,each of said nuclei being linked to the adjacent nuclei through 1-6sulfur atoms in sulphide linkages, said linkages being between carbonatoms of said nuclei selected from those carbon atoms ortho and para tosaid hydroxyl group, at least one of the terminal nuclei of said chaincontaining a chlorine atom, said compound containing about 50 to 62percent carbon, about 4.5 to 7.2 percent hydrogen, about 34 to 11percent sulfur, and about 16 to 5 percent chlorine, said compound havingan average molecular weight of about 500 to 740, and said compound beingsoluble in hydrocarbon mineral oil.

The novel sulfur and chlorine-containing reaction products of thisinvention possess a number of outstanding advantages. They veryeffectively improve the performance characteristics of a wide variety oforganic media adman...

when incorporated therein, for example, when used as additives inlubricating oil. Further, these products are readily prepared in goodyield from starting materials which are available as articles ofcommerce. Also, these products possess high solubility and compatibilitywith most organic media, especially petroleum hydrocarbon oils.Therefore, these products are easily blended with liquid hydrocarbonsand with other organic media and can be used at high concentrations,with no solubility problems occurring when liquid hydrocarbonscontaining these products are stored at low temperatures for longperiods of time. Furthermore, the products of this invention possessunusual resistance against hydrolysis and thus can be effectively usedas additives for organic media which come in contact with or containwater. Moreover, the products of this invention are very stable atelevated temperatures such as are encountered in operating gasolineengines. Thus when used as mineral oil additives for crankcaselubricants and the like no appreciable deterioration of the productsoccur during engme service.

Further, these compounds have the unusual advantage of possessingantioxidant properties as well as anti-wear and extreme pressureproperties. They also are used in their original form and need not becombined with metal lic salts. Advantages attendant with the use of suchproducts have not heretofore been achieved.

Another part of this invention is the process of preparing sulfur andchlorine-containing products which comprise reacting (1) a phenoliccompound having, ortho to the phenolic hydroxyl group, an alkyl group offrom 3-8 carbon atoms and (2) sulfur dichloride; there being at leastabout 1.0 mole of said sulfur dichloride per mole of phenol asreactants.

It is important that the molar concentration of the sulfur dichloridereactant be at least equivalent to the molar concentration of thealkylated phenol reactant. If concentrations of less than molarequivalence are used, an ineffective product results. For example, whenI use a product prepared from a reaction in which the molar ratio of SO1to phenol is 1.0, I obtain excellent antioxidant protection. There is nodefinite upper limit except that which is convenient. In other words, itis merely important to have a stoichiometric equivalent or excess ofsulfur dichloride present so as to insure complete reaction. Applicanthas found that excesses up to 1.5 molar ratio of sulfur dichloride toalkylated phenol result in reactions that are easy to control and yieldproducts which need no inordinate purification. The use of higheramounts will result in effective products but the presence of excessiveand unreacted sulfur dichloride gives rise to purification problems.Further, a slight excess would be desirable so as to insure completereaction with reasonable heating and reaction time. Accordingly, a molarratio of sulfur dichloride to alkyl phenol of from 1.1 to 1.5 isdesirable. Applicant has found that best results are obtained when aratio of about 1.5 is used.

In carrying out the present process hydrogen chloride gas is evolved. Itis, therefore, desirable to employ an inert solvent to act as a carrierand assist in the liberation of this gas. Suitable solvents for thispurpose include: hydrocarbons such as petroleum ether, hexane,isooctane, benzene, toluene, xylene, pseudocumene; inert chlorinatedhydrocarbons such as carbon tetrachloride, chloroform,trichloroethylene, chlorobenzene, ethylene dichloride, etc.; nitrohydrocarbons such as nitromethane, nitrobenzene, etc.; and the like. Thechoice of solvent should be such that the particular reactants employedwill be dissolved therein sufficiently to react effectively under theparticular reaction conditions.

The above reactions can be conducted conveniently from to 100 C. atreaction times of from a few minutes to about a day or more, such thatthe particular phenolic reactant chosen will effectively react to formthe desired product as described above. Reaction tem peratures of 15-65"C. have been found to be most convenient giving high yields in areasonable time. Further, reaction temperatures of 4065 C. arepreferable since excellent yields are obtained in a minimum of reactiontime. Applicant has found that by introducing the sulfur dichloridereagent over a period of time, for example, one hour at a temperature of40-45 C. and subsequently allowing the temperature to rise to 6065 C.for an additional hour produces the most favorable yields in areasonable time.

The reactions can be conducted in an open vessel. In commercialoperation Where recovery of the hydrochloric acid byproduct is desired,reaction may be conducted in a vessel equipped with such recovery means.Further, a nitrogen sweep may be used to aid in removing thehydrochloric acid gas.

The product obtained by the above process can be used very effectivelyby itself in various organic media without need of further purification.However, the compound can be increased in effectiveness and itssolubility in various media increased by the use of various treatments.

The products can be purified by washing with Na s, Na CO NaOH solutionsor mixtures thereof. Also the products can be purified by heat treatingthem to strip the volatiles. Another method of purification is todissolve the products in petroleum ether, filter the resultinginsolubles and subsequently strip the petroleum ether to yield thepurified product. A further method is to dissolve the product in mineraloil and filter the insol uoles from the mineral oil. If it is desired touse the products as an additive for lubricating oils, this lastprocedure is preferred. The products of this invention are highlysoluble and 50 weight percent can be dissolved in mineral oil. Afterfiltration of the insolubles a 50 weight percent mixture remains whichcan be incorporated directly into the lubricating oil. Furthercombinations of the above processes can be used. Thus the product can beheat treated, dissolved in mineral oil and the insolubles filtered toyield a 50 weight percent mixture of mineral oil and product. This lastprocedure is particularly preferred since it yields products which areexceptionally soluble and most highly effective as antioxidants,anti-wear and extreme pressure agents. Illustrations of the abovevarious treating procedures can be found in the ensuing examples.

Examples of the phenolic reactants used pursuant to this inventioninclude: Z-n-hexylphenol; Z-n-butylphenol; 2 sec-butylphenol;Z-tert-butylphenol; 2-(3-heptyl)phenol; 2-n-propylphenol;2-isopropylphenol; Z-n-amylphenol; 2-isobutylphenol and 2-n-octylphenol.

Preferred phenolic reactants are those having, ortho to the phenolichydroxyl group, an alpha-branched alkyl group having from 3-8 carbonatoms. These are preferred because of the ease of their reaction andsuperiority of the products obtained by their use. Examples of suchcompounds include: Z-isopropylphenol; 2- sec-butylphenol; 2-(3-octyl)phenol; Z-tert-amylphenol; 2- (2-heptyl)phenol; 2-(2'-hexyl)phenol and2-tert-octylphenol.

Thus another embodiment of this invention is a substantially involatile,reddish-yellow polynuclear phenolic material containing 2 to 5 phenolicnuclei wherein each phenolic nuclei contains one hydroxyl radical and analpha-branched alkyl group of 3-8 carbon atoms ortho to said hyd-roxylradical, said phenolic nuclei being linked together in a straight chain,each of said nuclei being linked to the adjacent nuclei through 1-6sulfur atoms in sulphide linkages, said linkages being between carbonatoms of said nuclei selected from those carbon atoms ortho and para tosm'd hydroxyl group, at least one of the terminal nuclei of said chaincontaining a chlorine atom, said compound containing about 50 to 62percent carbon, about 4.5 to 7.2 percent hydrogen, about 34 to 11percent sulfur, and about 16 to 5 percent chlorine,

said compound having an average molecular weight of about 500 to 740,and said compound being soluble in hydrocarbon mineral oil.

A particularly preferred phenolic reactant is 2-tertbu-ty-lphenol. Thisreactant is preferred because it is readily available, allows convenientreaction time and conditions and its use results in a most superior andefficacious product.

The antioxidant material prepared from Z-tert-butylphenol has certaincharacteristic analytical parameters. These products can be described asantioxidant material containing about 52 to 54 percent carbon, about 5to 5.5 percent hydrogen, about 24 to 12 percent sulfur, about 14 to 6percent chlorine and having a molecular weight of about 540 to 590. Thusa still further embodiment of this invention is a substantiallyinvolatile, reddishyellow polynuclear phenolic compound containing 2 to5 phenolic nuclei wherein each phenolic nuclei contains one hydroxylradical and one tertiary butyl group ortho to said hydroxyl radical,said phenolic nuclei being linked together in a straight chain, each ofsaid nuclei being linked to the adjacent nuclei through 1-6 sulfur atomsin sulphide linkages, said linkages being between carbon atoms of saidnuclei selected from those carbon atoms ortho and para to said hydroxylgroup, at least one of the terminal nuclei of said chain containing achlorine atom, said compound containing about 52 to 54 percent carbon,about 5 to 5.5 percent hydrogen, about 24 to 12 percent sulfur and about14 to 6 percent chlorine, said compound having a molecular weight ofabout 540 to 590, and said compound being soluble in hydrocarbon mineraloil.

The sulfur and chlorine-containing phenolic products of this inventionand the process for their preparation will be further apparent from thefollowing specific examples in which all parts and percentages are byweight, unless otherwise indicated.

EXAMPLE 1 In a reaction vessel equipped with stirring means, heatingmeans and temperature measuring means was placed a solution of 150 parts(1.0 mole) of 2 tert butylphenol in 315 parts of ethylene dichloride.The solution was stirred at 45 C. and a solution of 154 parts (1.5moles) of sulfur dichloride in 165 parts of ethylene dichloride wasadded over a period of 55 minutes. The temperature was allowed to riseto 60 C. and maintained at 60-65" C. during the addition and for onehour afterward. The solvent was distilled off at 89 mm. pressure to atemperature of 137 C. A resionous material resulted which will be calledproduct 1-A. A portion of product 1-A was then diluted with oil to 50weight percent and filtered hot through Celite filter-aid. This will becalled product 1-B and contains 50 percent active ingredient.

One hundred parts of product 1-A were stripped of volatiles up to 140 C.at 25 microns pressure. The loss amounted to three parts. The resultingproduct will be called product 1C. Total analysis of product 1-A is 52.5percent carbon, 5.39 percent hydrogen, 22.6 percent sulfur, 11.6 percentchlorine, 1.0 percent 2-tert-butyl-4- chlorophenol, 0.2 percent2-tert-butyl-6-chlorophenol and 0.9 percent2-tert-butyl-4,6-dichlorophenol. The molecular weight was found to be549'. Analysis of product l-C is 52.6 percent carbon, 5.46 percenthydrogen, 23.3 percent sulfur, 10.9 percent chlorine, 0.1 percent2-tertbutyl-4,6-dichlorophenol. Molecular weight was found to be 580.Polarographic analysis revealed the presence of polysulphides of atleast three sulfur atoms, and that about one-fourth of the sulfur waspresent as monosulphide and the rest as polysulphide.

EXAMPLE 2 In a reaction vessel equipped with stirring means, heating andcooling means, hydrochloric acid gas exit trap and temperature measuringmeans are added a solution 6 of 60 parts (0.4 mole) of Z-tert-butylphnolin 126 parts ethylene dichloride. The temperature was lowered to 1520 C.and maintained at that temperature while a solution of 46 parts (0.44mole) of sulfur dichloride in 63 parts of ethylene dichloride was addedover a period of 1.25 hours. The mixture was allowed to come to roomtemperature, about 23 C., then heated to 35 C. and maintained at thattemperature for one hour. Hydrochloric acid was collected in the gasexit trap and amounted to 75 percent of theory. Volatiles were strippedfrom the reaction mixture at about 9095 C. under aspirator pressure toobtain a reddish-yellow resin of this invention. Analysis: 19.5 percentsulfur, 8.17 percent chlorine.

EXAMPLE 3 The procedure of Example 2 was repeated yielding areddish-yellow resin analyzing 21.6 percent sulfur and 10.7 percentchlorine. This will be called product 3-A. A 40-part portion of product3-A was treated with 260 parts of petroleum ether (boiling point of38-40 C.) which dissolved all but a small residue. The residue wasrecovered by filtration and the solvent was stripped, leaving 31.4 partsof a resinous semisolid of this invention. This will be called product3-B. Analysis: 21.1 percent sulfur, 11.5 percent chlorine.

Another portion of product 3-A was diluted with benzene and washedsuccessively with cold water, a solution containing 10 parts sodiumhydroxide, 10 parts sodium sulphide and par-ts water, a 10 percentaqueous sodium hydroxide solution and cold water to neutrality (4 washeswere needed). The product was dried and then stripped at 0.5 mm., 25 C.to a constant weight. Analysis: 12.5 percent sulfur, 12.3 percentchlorine. This will be called product 3-C.

EXAMPLE 4 In a reaction vessel equipped with stirring means, heating andcooling means, temperature measuring means, gas inlet and outlet tubes,hydrogen chloride gas exit trap and a nitrogen source were placed 150parts (1.0 mole) of 2-tert-butylphenol in 189 parts of ethylenedichloride. The vessel was flushed with nitrogen and the temperaturelowered to 1520 C. One hundred thirteen and three tenths (1.1 moles)parts of sulfur dichloride in 15 1 pants of ethylene dichloride wereadded dropwise over a period of 1.5 hours with stirring. The temperaturewas raised to room temperature, about 25 C., then heated to 35 C. andmaintained at that temperature with stirring for one hour. Hydrogenchloride gas, amounting to 73 ercent of theory, was trapped in the gasexit trap. The mixture was then stripped at reduced pressure yielding adark reddish-yellow transparent resin. Two hundred forty parts ofpetroleum ether (boiling point of 3840 C.) were added and the mixturewas stirred until only a small amount of insoluble material remained. Anadditional 320 parts of petroleum ether were added to insure completeextraction from the insoluble material and to facilitate handling. Themixture was filtered and stripped of solvent at 95 C. under aspiratorpressure yielding a reddish-yellow resin residue of this invention.Analysis: 221 percent sulfur, 6.55 percent chlorine. Infrared analysisshowed the spectrum to be qualitatively identical to the spectrum of theproduct of Example 3.

Fifty parts by volume of the above product were dissolved in 50 parts byvolume of mineral oil at about 90'- C. The material remained in oilsolution after standing for 48 hours with no separation or precipitationobserved. The oil solution was heated at 9095 C. for 40 minutes with apolished copper strip. The strip remained essentially untarnished.

EXAMPLE 5 To demonstrate the unobvious and unexpected properties of theproducts of applicants invention, two materials were prepared fallingoutside the scope of applicants invention.

One product, which shall be called -A, was prepared by reacting 150parts (1 mole) of 4-tert-butylphenol with 113.3 parts (1.1 moles) ofsulfur dichloride following the procedure of Example 4.

Another product, which shall be called 5-8, was prepared by reacting 150parts (1 mole) of Z-tert-butylphenol with 92.63 parts (0.9 mole) ofsulfur dichloride following the procedure of Example 4. Thus, product5-A is in all respects the same as the product of Example 4 except thestarting material is 4-tert-butylphenol instead of Z-tert-butylphenol.Also product 5-B is in all respects the same as the product of Example 4except the molar ratio of sulfur dichloride to phenol is 0.9, whereasthe corresponding molar ratio of the product of Example 4 and of 5A is1.1.

Products 5-A, 5B and the product of Example 4 were tested in a modifiedPolyveriform oxidation stability test. The normal Polyveriform oxidationstability test is described in the paper entitled Factors CausingLubricat ing Oil Deterioration in Engines, Ind. and Eng. Chem, anal. ed.17, 302 (1945). See also A Bearing Corrosion Test for Lubricating Oilsand Its Correlation With Engine Performance, Anal. Chem. 21, 737 (1949).This test evaluates the performance of lubricating oil antioxidants. Thetest equipment and procedure employed are discussed in the first papercited above.

One modification was that the steel sleeve and copper test piecedescribed in this publication were omitted from the apparatus. In thesetests an initially additive-free, 105.5 V.I. solvent-refined SAE-crankcase oil was used. The principal conditions consisted of passing 48liters of air per hour through the test oil for a total period of 120hours while maintaining the oil at a temperature of 300 F. Oxidativedeterioration of the oil was further promoted by employing as oxidationcatalysts 0.10 percent by weight of lead bromide, based upon the weightof oil employed. In addition a copper lead bearing is submerged in theoil as an additional catalyst. At the end of the test the loss in Weightof the copper lead bearing is determined. When no loss in weight hasoccurred, a small increase in weight is generally observed. Thisincrease in weight is generally within the experimental error of thetest. It can also be attributed to the formation of a slight amount ofvarnish which is expected from the harsh conditions of the test. Such adetermination gives good correlation with actual engine tests.

Lubricating oils were prepared by blending 0.5 weight percent ofefiective compound, based on the weight of the test oil, with individualportions of the test oil. These compositions were then subjected to theabove stringent oxidation test. The results are shown in Table I. Thenature of the reactants and ratios of sulfur to phenol are also given inthe table.

Table 1 EFFECT ON A COPPER-LEAD BEARING IN LUBRICAT- ING OIL (0.5 WEIGHTPERCENT EFFECTIVE COM- PONENT) 1 An average of two tests.

It can be seen from the data that products having the same reactants butin a molar ratio of 0.9: 1 are ineffective. Further, products having thesame molar ratio but an isomeric reactant are ineffective. Thus thesuperiority of applicants invention is completely unobvious andunexpected.

EXAMPLE 6 In a reaction vessel equipped with stirring means, heating andcooling means, hydrochloric acid gas exit trap and temperature measuringmeans were placed a solution of 300 parts (2.0 moles) of2-tert-butylphenol in 630 parts of ethylene dichloride. The solution wasstirred at 1520 C. and maintained at that temperature while a solutionof 268 parts (2.6 moles) of sulfur dichloride in 286 parts of ethylenedichloride was added over a period of one hour. The mixture was allowedto come to room temperature, about 25 C., and then heated to 35 C. andmaintained at that temperature for one hour. Hydrochloric acid wascollected in the gas exit trap and amounted to 83.5 percent of theory.The volatiles were stripped from the reaction mixture at about 9095 C.under aspirator pressure to obtain a reddish-yellow resin. Analysis:20.5 percent sulfur, 11.7 percent chlorine. This product will be called6-A.

The above procedure was repeated except that the temperature at whichthe sulfur dichloride was added was maintained at 4045 C. Analysis: 20.4percent sulfur, 7.5 percent chlorine. The amber colored resin producedwill be called 6-B.

The above procedure was repeated again except that the temperatureduring addition of the sulfur dichloride was maintained at 65 C. Theclear amber colored resin produced will be called 6C.

Again the last-described procedure was repeated, that is, thetemperature at which sulfur dichloride was added was maintained at 6065C. The resinous product was diluted with benzene and washed successivelywith cold water, a 10 percent aqueous sodium carbonate solution and coldwater to neutrality. The product was dried and then stripped at 0.5 min,25 C., to a constant weight. This will be called 6-D.

In order to demonstate the consistent antioxidant effectiveness of theproducts produced by this invention Within the preferred range of thereaction conditions, the modified Polyveriform oxidation stability testdescribed in Example 5 was run using the products 6A, B, C and D. Thefollowing table summarizes the results.

Table II EFFECT OF REACTION VARIABLES ON ANTIOXIDANT ACTIVITY (0.5\VEIGHT PERCENT EFFECTIVE COM- .PONENT) [Molar ratio of 1.31-sulfur-dichloride/pheno1] Preparation Bearing Product Temperature,Treatment Weight 0. Loss, mg.

60-65 NtlzCO3 Wash 1 As can be seen from the table the products of thisinvention show uniform results within the experimental error of thetest. A comparison with the results for Example S-A and 5-B in Table Iimmediately reveal the superiority of all the products 6A-D.

EXAMPLE 7 tion results which has excellent oil solubility andantioxidant properties.

EXAMPLE 8 In a reaction vessel equipped with stirring means, heating andcooling means and temperature measuring means are placed 272 parts (2moles) of o-isopropylphenol in 480 parts of iso-octane. The solution isheated to 40 C. and maintained at that temperature While a solution of288 parts (2.8 moles) of sulfur dichloride in 210 parts of iso-octane isadded over a period of 20 minutes. The mixture is heated for anadditional 30 minutes. Volatiles are stripped from the reaction mixtureat about 90-95 C. under aspirator pressure. The residue is then treatedwith 1,000 parts of petroleum ether (boiling point of 38- 40 C.) Theresulting solution is filtered and the solvent is stripped leaving aresinous material of this invention which has excellent anti-wearingproperties.

EXAMPLE 9 In a reaction vessel equipped with stirring means, heating andcooling means and temperature measuring means is placed a solution of206 parts (1.0 mole) of 2-(3'- octyl) phenol in 320 parts ofnitrobenzene. The mixture is heated to 60 C. and maintained at thattemperature while a solution of 206 parts (2.0 moles) of sulfurdichloride in 140 parts of nitrobenzene is added over a period of onehour. The mixture is then heated to 100 C. and maintained at thattemperature for 24 hours. The volatiles are then stripped under reducedpressure to yield a resinous material of this invention which hasexcellent anti-wear properties.

The above procedures is repeated using as the phenol reactants2-sec-butylphenol. The product of this invention which results hasexcellent antioxidant properties.

EXAMPLE 10 In a reaction vessel equipped with stirring means, heatingand cooling means and temperature measuring means are placed a solutionof 750 parts (5.0 moles) of 2-isobutylphenol in 1,000 parts ofiso-octane. The solution is heated to 50 C. and maintained at thattemperature while a solution of 565 parts (5.5 moles) of sulfurdichloride in 440 parts of iso-octane is added over a period of 120minutes. The temperature is then raised to 70 C. and maintained at thattemperature for 10 hours. The temperature is then raised to 95100 C. andstripped of volatiles under aspirator pressure. A clear, reddishyellowresinous solid of this invention results which has excellent extremepressure properties.

EXAMPLE 11 In a reaction vessel equipped with heating and cooling means,stirring means, temperature measuring means, gas inlet and outlet tubesand a nitrogen source are placed a solution of 178 parts (1.0 mole) of2-('-2- hexyl)phenol in 250 parts of chlorobenzene. The vessel isflushed with nitrogen, the temperature raised to 65 C. and maintained atthat temperature while a solution of 175 parts (1.7 moles) of sulfurdichloride in 110 parts of chlorobenzene is added dropwise over a periodof 45 minutes with stirring. The mixture is heated for an additional 2hours at 65 C. while nitrogen is swept through the vessel. The mixtureis then heated to 130 C. under aspirator pressure and stripped ofvolatiles. A resinous material results which is diluted with benzene andwashed successively with cold water, a solution containing 10 partssodium hydroxide and cold water to neutrality. The material is dried andthen stripped at 0.5 mm., 25 C., to a constant weight. The product ofthis invention has excellent solubility, antioxidant and anti-wearproperties.

The above procedure is repeated using the phenolic reactant2-n-propylphenol. The resulting product of this invention has excellentsolubility, antioxidant, anti-wear and extreme pressure properties.

10 EXAMPLE 12 To the reaction vessel of Example 7 is added a solution of82.0 parts (0.5 mole) of Z-tert-amylphenol in 120 parts of toluene. Thesolution is heated with stirring to 4045 C. A solution of 8 2.4 parts(0.8 mole) of sulfur dichloride in parts of toluene is added dropwiseover a period of 60 minutes. The temperature is allowed to rise to 6065C. and maintained during the addition and for 5 hours afterward. Thetemperature is then raised to 95 C. and volatiles are removed under reduced pressure. A resinous reddish yellow solid of this inventionresults which can be used as an oil antioxidant.

EXAMPLE 13 In a reaction vessel equipped with stirring means, heatingand cooling means and temperature measuring means is placed a solutionof 51.5 parts (0.25 mole) of 2-tertoctylphenol in 70 parts of carbontetrachloride. The mixture is cooled to 15 C. and maintained at thattemperature while a solution of 46.4 parts (0.45 mole) of sulfurdichloride in 40 parts of carbon tetrachloride are added over a periodof 55 minutes. The temperature is then raised to 80 C. and the mixturestirred at that temperature for 2 hours. The mixture is subjected toreduced pressure at that temperature and the volatiles removed. Aresinous solid of this invention results which imparts stability tolubricating oil.

The above procedure is repeated using as the phenol reactant2-n-octylphenol. The product of this invention which results hasexcellent solubility and antioxidant properties and can be incorporatedinto a Wide variety of organic media.

EXAMPLE 14 To the reaction vessel of Example 13 is added a solution of164 parts (1.0 mole) of 2-n-amylphenol in 280 parts of xylene. Thetemperature is lowered to 10 C. and stirred at that temperature while asolution of 196 parts (19 moles) of sulfur dichloride in 180 parts ofxylene is added over a period of 20 minutes. The mixture is then heatedto 30 C. and maintained at that temperature with stirring for one hour.The temperature is then raised to 70 C. and the solvent distilled offunder reduced pressure. A resinous material of this invention resultswhich has excellent anti-wear properties.

The above material is diluted with an equal weight of mineral oil,heated to about C. and filtered through Celite-filter air resulting inan oily product of this invention containing 50 percent activeingredient.

When various phenols are reacted in accordance with this invention theproduct obtained has a carbon, hydrogen, sulfur, chlorine and molecularweight analysis in the ranges of 50 to 62 percent carbon, 4.5 to 7.2percent hydrogen, 34 to 11 percent sulfur, 16 to 5 percent chlorine and500 to 740 molecular weight.

The products of this invention are outstanding antioxidants. Therefore,an embodiment of this invention is a new composition of matter whichcomprises organic material normally tending to undergo oxidativedeterioration in the presence of air, oxygen or ozone, containing anappropriate quantity, from 0.001 up to about 5 percent, and preferablyfrom about 0.25 to about 2 percent, of a product of this invention.

The products of this invention find important utility as antioxidants ina wide variety of oxygen sensitive mate-, rials. Thus, liquidhydrocarbon fuels such as gasoline, kerosene and fuel oil are found topossess increased storage stability by the use of a product of thisinvention. Likewise, liquid hydrocarbon fuels such as gasoline whichcontain organometallic additives such as tetraethyllead, as well asother orgauometallic compounds which are used as fuel additives, attainappreciably increased oxidative stability by the practice of thisinvention. In addition, lubricating oils and functional fluids, boththose derived from naturally occurring hydrocarbons and those synthetically prepared, are greatly enhanced by the practice of thisinvention. The addition of small quantities of the products of thisinvention to such materials as turbine, hydraulic, transformer and otherhighly refined industrial oils, waxes, soaps and greases, plastics,synthetic polymers such as polyethylene and polypropylene,organometallic compositions such as tetraethyllead and tetraethylleadantiknock fluids, elastomers (including natural rubber), crankcaselubricating oils, lubricating greases, and the like, greatly increasetheir resistance to deterioration in the presence of air, oxygen orozone.

The products of this invention are also very effective antioxidants forhigh molecular weight unsaturated hydrocarbon polymers, such aspolybutadiene, methyl rubber, polybutene rubber, natural rubber, butylrubber, GR-S rubber, GR-N rubber, piperylene rubber, dirnethyl butadienerubber and the like.

As noted, the products of this invention are useful in preventingoxidative deterioration in lubricating oil compositions. Thus, apreferred embodiment of this invention is a lubricating oil normallysusceptible to oxidative deterioration containing a small antioxidantquantity, up to 5 percent, of a product of this invention as definedabove.

To prepare the lubricants of this invention, an appropriatequantity-from about 0.001 to about 5 percent and preferably from about0.25 to about 2 percent-of a product of this invention is blended withthe base oil to be protected. Suitable base oils include mineral oilsand also synthetic diester oiis, such as sebacates, adipates, etc. whichfind particular use as aircraft instrument oils, hydraulic and dampingfluids and precision bearing lubricants. All of these base oils arenormally susceptible to oxidative deterioration, especially at elevatedtemperature.

The finished lubricants of this invention have much greater oxidationstability and many other improved performance characteristics ascompared witht 1@ correspond ing base oils. The following examplesillustrate the preferred lubricating oil compositions of this invention.

EXAMPLE 15 To illustrate the outstanding advantages achieved by thepractice of the preferred embodiments of this invention, particularlywhen the compositions are subjected to elevated temperature, experimentswere conducted using the panel coker test. This test measures theoxidative stability of oils which are maintained at elevatedtemperatures in the presence of air, the oils periodically coming incontact with a hot metal surface. The test is described in theAeronautical Standards of the Departments of Navy and Air Force, Spec.MlLL7808c, dated November 2, 1955. In these tests an initiallyadditive-free 95 V1. solvent-refined SAE 10 crankcase oil was used. Thepanel coker apparatus was operated at 600 F. for 10 hours on a cyclingschedulethe splasher being in operation for 5 seconds followed by aquiescent period of seconds. On com letion of these tests the extent bywhich the various test oils were decomposed under these high-temperatureoxidizing conditions was determined by weighing the amount of depositwhich formed on the metallic panel. The results are given in Table III.

Table III PANEL COKER DATA Panel Weight Gain, mg.

Concentration, Percent Additive None Product 3B tive deterioration.

12 EXAMPLE 16 As a further illustration of the advantages achieved bythe practice of this invention a standard Polyveriform test Was run. Thetest conditions are described in the references discussed in Example 5.The present test is not modified as was the one in Example 5. This testeifectively evaluates the performance of lubricating oil antioxidants.The procedures employed and correlations of the results with engineperformance are discussed in the first-named paper in Example 5. As inExample 5 a modification was that the steel sleeve and copper test piecedescribed in the publication were omitted from the apparatus. In itsplace .05 percent by weight of the test oil of ferric oxide (as ferricZ-ethylhexoate) and 0.10 percent by weight of the test oil of leadbromide were added as oxidation catalysts. In these tests an initiallyadditive-free V1. solvent-refined SAE 10 crankcase oil was used. Theprincipal test conditions consisting of passing 48 liters of air perhour through the test oil for a total period of 20 hours whilemaintaining the oil at a temperature of 300 F.

Lubricating oils of this invention were prepared by blending products ofthis invention with the oil described above. These compositions werecompared in the Polyveriform test with a sample of the oil notcontaining an antioxidant. As can be seen from the results listed inTable IV oils containing a product of this invention gave much superiorresults than base oils containing no additive.

To illustrate the anti-wear and extreme pressure properties of theproducts of this invention a lubricant composition of this invention wastested in a four ball extreme pressure machine to determine thelubricity of the respective lubricant compositions relative to a baseline of the unprotected lubricant. The four ball extreme pressuremachine is described by Lawson and Perry in the Transactions of theA.S.M.E., January 1945, pp. 45-50. The machine operates in the loadrange of 40 to 800 kilograms.

The four ball extreme pressure machine utilizes four balls of equal sizearranged in an equilateral tetrahedral formation. The bottom three ballsare held in a nonrotatable ball holder which is essentially a universalchuck that holds the balls in abutting relation to each other. Since thebottom three balls are of equal size the centers form the apices of anequilateral triangle. The top ball is aflixed to a rotatable spindlewhose axis is positioned perpendicular to the plane of the ball holderand in line with the center point of the triangle whose apices are thecenters of the three bottom stationary balls. In operation, the fourballs are immersed in the lubricant composition to be tested and theball holder is moved upwardly so as to bring the three fixed lower ballsinto engagement with the upper rotating ball. As the load is increased,the ball holder is moved upwardly and axially of the rotating spindleafiixed to the upper ball.

The lubricity of the lubricant under test is determined by the amount ofwear occurring at the contact points between the three upper rotatingballs and the three fixed lower balls under the conditions of the test.If the lubricant is completely effective, the amount of wear will besmall. On the other hand, if the lubricant is not completely effectiveunder the test conditions, the upper ball may fuse or weld to the lowerballs due to heat or friction at the contact points or the upper ballmay form circular scars in the lower balls along their line of contact.If scars are formed in the lower balls the average diameter of thecircular scar is measured so as to give a quantitative basis forcomparing the test results with those of other tests in which circularscars were formed. As the severity of the test conditions are increasedwith a given lubricant com position the likelihood of scarring the lowerballs is increased. Thus the formation of scars does not indicate thatthe lubricant composition is unsatisfactory but rather serves only toindicate its degree of effectiveness under certain test conditions.

In the present test the ball afiixed to the rotatable spindle isrotating at 1800 rpm. Separate tests were conducted at loads of from 40to 150 kilograms, each test lasting one minute. The results are listedin Table V.

Table V FOUR BALL EXTREME PRESSURE TEST Referring to Table V it can beseen that the presence of an additive compound of this invention inlubricating oil substantially reduces the amount of scar on the steelballs used in the test. Further, while the unprotected oil welded at aload of 120 kilograms the lubricant composition or" this invention didnot weld even after a load of 150 kilograms was applied.

EXAMPLE 18 To 1,000 parts of a solvent refined neutral oil (95 V1. and200 SUS at 100 F.) containing 6 percent of a commercial methacrylatetype V.I. improver which gives the finished formulation of a V.I. of 140and a viscosity of 300 SUS at 100 F. is added percent of the product ofExample 14.

EXAMPLE 19 To an additive-free solvent refined crankcase lubricating oilhaving a viscosity index of 95 and an SAE viscosity of is added 0.001percent of product 1-A.

EXAMPLEVZO To 100,000 parts of a petroleum hydrocarbon oil having agravity of 303 API at 60 F., viscosity of 178.8 SUS at 100 F., aviscosity index of 154.2 and which contains 0.2 percent sulfur, is added200 parts of product 6 D. The resulting oil possesses greatly enhancedresistance to oxidative deterioration and possesses excellent Wearproperties.

EXAMPLE 21 To 100,000 parts of a commercially available pentaerythritolester having a viscosity at 100 F., of 22.4 centistokes, and known inthe trade as Hercofiex 600 is added 400 parts (0.4 percent) of theproduct of Example 8. The resulting finished oil possesses markedlyimproved resistance against oxidative deterioration, and has excellentwear properties.

EXAMPLE 22 To 100,000 parts of a dioctyl sebacate having a viscosity of210 F., of 36.7 SUS, a viscosity index of 159 and a molecular weight of426.7 is added 250 parts (0.25 percent) of product 1-B.

The saturated hydrocarbon synthetic polymers which achieve greatlyenhanced oxidative stability by the practice of this invention, includepolymers obtained from the polymerization of a hydrocarbon monoolefinhaving up to 4 carbon atoms. Examples of such monomers are ethylene,propylene, butene-l, butene-Z and isobutylene. Thus the polymers arehomopolymers and copolymers of ethylene, propylene, butane-1, butene-Zand isobutylene.

The concentration of the products of this invention in the polymers isfrom 0.001 up to 5 percent, and preferably from about 0.25 to about 2percent.

Polyethylene is a hydrocarbon polymer derived from the polymerization ofethylene. This polymerization can be accomplished by a great variety ofmethods which lead to products of diverse properties. Polyethylene ofany nature may advantageously be utilized for preparing compositionsaccording to the present invention. The polymers of ethylene which areemployed may, for example, be similar to those which may be obtained bypolymerizing ethylene in a basic aqueous medium and in the presence ofpolymerization-favoring quantities of oxygen under relatively highpressures in excess of 500 or 1,000 atmospheres at temperatures between150 and 275 C. Or, if desired, they may be similar or identical to theessentially linear and unbranched polymers ordinarily having greatermolecular weights which may be obtained under relatively low pressuresof 1 to atmospheres using such catalysts to polymerize the ethylene asmixtures of strong reducing agents and compounds of groups IVB, VB andVIB metals of the periodic system; chromium oxide on silicated alumina;hexavalent molybdenum compounds; and charcoal supported nickel-cobalt.

The polyethylene which results from these various polymerizationprocesses may have a molecular weight in the range from 1300 to over1,000,000 depending on the particular conditions of polymerizationemployed.

There are several methods available for preparing the inhibitedhydrocarbon polymer compositions of this invention. Thus, the blendingof the antioxidant with a polymer such as, for example, polyethylene,may be carried out on open rolls, on internal mixers or may beaccomplished by mixing with extrusion. It is also possible to prepareconcentrated batches of the polymer containing excessive amounts of theantioxidant and then mix the concentrate with additional polymer toprepare a composition of this invention. The preferred method ofcompounding the polymers is by milling on heated open rolls at slightlyelevated temperatures by methods wellknown to the art. The temperaturerange employed is sometimes critical as certain polyethylenes will notmelt at low temperatures and tend to stick to the rolls at hightemperatures. The antioxidant may be initially mixed with the polymer inthe dried state or it may be first dissolved in a suitable solvent, thensprayed on the polymer and milled in.

Examples of the hydrocarbon polymer compositions of this inventionprepared as described above, follow. All parts and percentages are byWeight in these examples.

EXAMPLE 23 To 1,000 parts of polyethylene produced by oxygen catalyzedreaction under a pressure of 20,000 atmospheres and having an averagemolecular weight of 40,000 is added and mixed 2 parts of the product ofExample 10. The resulting composition has greatly increased oxidativestability.

EXAMPLE 24 With 200 parts of polyisobutylene having an average molecularweight of 100,000 is blended 1.0 part of product 6-A.

EXAMPLE 25 To a master batch of high molecular weight polyethyl- 15 enehaving an average molecular weight of about 1,000,000, a tensilestrength of 6,700 p.s.i., a Shore D hardness of 74 and a softeningtemperature under low load of 150 C. is added percent of the product ofExample 12.

EXAMFLE 26 A linear polyethylene having a high degree of crystallinity(about 93 percent) and below 1 ethyl branched chain per hundred carbonatoms, a density of about 0.96 gram per milliliter and which has about1.5 double bonds per 100 carbon atoms is treated with 50 10- roentgensof fl-radiation. To the thus irradiated polymer is added 0.005 percentof the product of Example 7 and the resulting product has betterstability characteristics.

EXAMPLE 27 To a polyethylene having an average molecular weight of 1500,a melting point of 88-90" C. and a specific gravity of 0.92 is added 1percent of product 1C. After milling in the antioxidant an extremelyoxidation resistant product results.

EXAMPLE 28 Two parts of the product of Example 13 are added with millingto 100 parts of a low density polyethylene prepared by high pressurepolymerization and which has an average molecular weight of about20,000. The resulting product is vastly improved in its oxidativestability.

EXAMPLE 29 To 10,000 parts of a polyethylene having an average molecularweight of about 100,000 and which has a tensile strength of 5400 p.s.i.,a Shore D hardness of 70 and a softening temperature of 130 C. under lowload is added parts of product 6-8 to prepare a composition ofoutstanding oxidative stability.

EXAMPLE 30 To the polyethylene in Example 17 is added 0.05 percent ofthe product of Example 11. The resulting composition has improvedantioxidant characteristics.

EXAMPLE 3 1 To a polyisobutylcne polymer having an average molecularweight of 35,000 is added a sufficient amount of product 6C to give acomposition containing 0.03 percent of the antioxidant. The compositionhas improved antioxidant properties due to the presence of product 6C.

EXAMPLE 32 To a polypropylene having a specific gravity of 0.90, atensile strength of 4300 p.s.i., a Rockwell hardness of 8S and a heatdistortion temperature of 210 F. under a pressure of 66 psi. is added0.06 weight percent of the product of Example 4. The resulting polymeris stable against the deleterious eilects of oxygen.

EXAMPLE 3 3 To a polybutene, prepared from the polymerization ofbutene-l, and having an average molecular weight of 15,000, is added0.15 weight percent of the product of Example 9 give a polymer ofoutstanding oxidation stability.

EXAMPLE 34 To a polybutene, prepared from the polymerization ofbutene-2, and having a molecular weight of 25,000 is added 0.10 weightpercent of product 1-A to yield a polymer with exceptional oxidativestability.

EXAMPLE 35 To the polyisobutylene polymer of Example 31 is added 0.07percent of the product of Example 10.

16 EXAMPLE 36 To the polypropylene of Example 32 is added 0.02 percentof product 3-C.

EXAMPLE 37 To the polybutene of Example 33 is added 0.03 percent ofproduct 3-C.

EXAMPLE 38 To the polybutene of Example 34 is added 0.08 percent of theproduct of Example 14.

In addition to an antioxidant product of this invention the saturatedhydrocarbon polymers of this invention may contain other compounding andcoloring additives including minor proportions of carbon black,elastorners, polyvinyl compounds, carboxylic acid esters, urea-aldehydecondensation products, flame retarding agents such as antimony trioxideand chlorinated hydrocarbons and various pigment compositions designedto impart color to the finished product.

The products of this invention are very useful in protecting petroleumwax-parafiin Wax and micro-crystalline waxagainst oxidativedeterioration. They also find use in the stabilization of edible fatsand oils of animal or vegetable origin which tend to become rancidespecially during long periods of storage because of oxidativedeterioration. Typical representatives of these edible fats and oils arelinseed oil, cod liver oil, castor oil, soybean oil, rapeseed oil,coconut oil, olive oil, palm oil, corn oil, sesame oil, peanut oil,babassu oil, butter fat, lard, beef tallow and the like.

The products of this invention are also very useful in protectingvitamins against degradation, especially those vitamins which areincorporated in an oil base. Thus an embodiment of this invention isvitamins protected from degradation by incorporating said vitamins intoan oil base containing a compound of this invention.

The products of this invention are also useful as additives tofunctional fluids and automatic transmission fluids. The primaryconstituent of a functional fluid is a refined mineral lubricating oilhaving a carefully selected minimum viscosity of 49 Saybol-t Universalseconds (SUS) at 210 F. and a maximum viscosity of 7,000 SUS at 0 F.,generally a distillate oil, lighter than an SAE 10 motor oil. The oilusually amounts to between about 73.5 to about 97.5 percent by weight ofthe finished fluid. Preferably, the base oil is selected from a paraflinbase distillate such as a Pennsylvania crude.

The fluids usually contain compounds which are characterized bycontaining one or more organic components which may be alkyl, aryl,alkaryl or aralkyl groups that are bonded to one or more metal atomsthrough coupling groups such as sulfonate, hydroxyl, carboxyl andmercaptan. The metal atoms may be aluminum, calcium, lithium, barium,strontium, and magnesium. The organic components contain oilsolubilizing groups such as high molecular weight straight or branchedchain paraffins, aromatic or naphthenic rings, or contain a halogen.These metal compounds are present in the compounded fluid in aconcentration range of between about 0.1 to about 5 percent by weight.These compounds include alkaline-eanth metal salts or phenyl-substitutedlong chain fatty acids, alkaline-earth metal salts of the capryl oroctyl esters of salicylic acid, the alkalineearth metal salts ofpetroleum sulfonic acids, the alkaline-earth metal salts ofalkyl-substituted phenol sultides, the salt of aluminum or thealkaline-earth metals with cetyl phenol, and the metal salts ofwax-substituted phenol derivatives. Another class of additives are theso-called overbased phenates and sulfonates, which can be prepared byreaction between an alkyl phenol or alkyl phenol sulfide and analkaline-earth metal oxide or hydroxide at an elevated temperature. Theoverbased 1 7 phenate formed from the reaction contains up to two orthree times as much metal as the normal phenate.

In addition, functional fluids may contain additional components whichimprove the properties of the fluid. Typical components includeanti-squa wk additives, pour point depressants, foam inhibitors, rustpreventatives, extreme pressure agents, metal deactivators and viscosityindex improvers.

The following examples show typical functional fluids of this invention.The fluids are formed by mixing the ingredients together, While heatingthe oil to a temperature up to 200 F.

EXAMPLE 39 A fluid of this invention is prepared by blending 80 parts ofa conventionally-refined Pennsylvania mineral oil (99 SUS at 100 F.), 2parts of product 1-C, 5 parts of barium petroleum sulfonate, parts of apolyacrylate having a molecular weight of approximately 7,000 derivedfrom a fatty alcohol such as cetyl or lauryl alcohol, 0.1 part of adimethyl silicone polymer anti-foam agent, 2 parts of a dialkyl zincdithiophosphate and 0.9 part of a dark, viscous liquid having aviscosity of 560 SUS at 210 F., a flash point of 420 F., a pour point of30 F. and a specific gravity of 60/ 60 F. of 0.919.

EXAMPLE 40' Another such fluid consists of 95 parts of a solventrefined, light acid-treated, clay-contacted, solvent dewaxed paraflinbase distillate mineral oil (110 SUS at 100 'F.); 0.1 part of theproduct of Example 9, 0.1 part of calcium octylphenol sulfide; 2 partsof a sulfurized sperm oil having a sulfur content between 10-12 percent,a viscosity of 210 F. of 200 SUS and a pour point of 65 F; 0.3 part ofan ester of an aromatic acid and waxalkylated phenol having a molecularWeight of approximately 450; 2.5 parts of a linear pale colorisobutylene polymer of a controlled molecular weight having a viscosit'yof 3,000 SUS at 210 F., a specific gravity of 60/60 of 0.875.

Liquid hydrocarbon fuels employed in the operation of spark ignitioncombustion engines are also vastly improved in their storage ability bythe practice of this invention. Table VI, below, gives the compositionsof a number of typical commercial gasolines which may be stabilizedagainst oxidative deterioration by the inclusion therein of a product ofthis invention.

7 To 1,000 parts of gasoline A, as described in Table V1, is added 10parts of product 6-A.

EXAMPLE 42 To 10,000 parts of gasoline B is added 50 parts of product1-B.

EXAMPLE 43 To 500 arts of gasoline C, as described in Table V1, is added10 parts of product 3-A.

EXAMPLE 44 To 2,000 parts of gasoline D is added parts of the product ofExample 7.

18 EXAMPLE 45 To 10,000 parts of gasoline E is added 500 parts of theproduct of Example 13.

Antiknock compositions and spark ignition internal combustion enginefuels containing mixtures of organolead antiknock agents andcyclopentadienyl manganese tricarbonyls are also vastly improved intheir storage stability by the practice of this invention. Such ompositions are described more fully in US. Patent No. 2,818,- 417.

In the compositions of this invention the concentrations of the primeingredients will vary. Thus the finished fuels of this invention cancontain from about 0.2 to about 6.4 grams of lead per gallon as anorganolead antiknock agent. The manganese or nickel concentrationstherein can range from about 0.005 to about 6 grams per gallon as acyclopentadienyl manganese tricarbonyl or cyclopentadienyl nickelnitrosyl respectively. On a cost effectiveness basis, finished motorfuels containing per gallon from about 1 to about 4 grams of lead andfrom 0.05 to about 2 grams of manganese or nickel are preferred. In allof these finished fuels the concentration of the above compounds ofthis. invention can be from about 0.0002 to about 0.01 Weight percentbased on the fuel. Expressed in different units these concentrationscorrespond respectively to about 0.5 to about 25 pounds per thousandbarrels of fuel. These concentrations are sulficient to inhibit thedeterioration which would occur in the absence of the compounds of thisinvention.

In formulating finished fuels it is common practice to employconcentrated gasoline solutions of the additives. These stock solutionsare then cut with or metered into the remainder of the gasoline toachieve the appropriate concentration in the finished fuel. A feature ofthis invention is that such concentrated stock solutions are likewisevery effectively stabilized by the presence therein of the abovecompounds of this invention. Consequently, the concentrations of theabove ingredients can be as much as 10 times as high as those set forthabove. The choice of concentrations is within the discretion of therefiner and takes into consideration the quantities of gasoline beingprocessed, the storage temperatures to be accounted, the length ofstorage involved, etc. The specific concentrations given above are forillustrative purposes only and are not to be considered as limitationsupon this invention.

Another embodiment of this invention is an antiknock fluid compositionadopted for use as an additive to gasoline, which composition consistsessentially of an organolead antiknock agent, a cyclopentadienylmanganese tricarbonyl or cyclopentadienyl nickel nitrosyl and a productof this invention as defined above, there being present in thecomposition from about 0.00078 to about 30 parts by weight of manganeseor nickel per part of lead and from about 0.001 to about 5 weightpercent of the compounds of this invention based on the weight of theorganolead antiknock agent. These compositions possess greater stabilityby virtue of the presence therein of a compound of this invention.Furthermore, these compositions provide an excellent vehicle by whichthe finished fuels of this invention can be formulated.

The foregoing compositions of this invention can also contain otheradditives known in the art. Halogen scavengers for the organoleadantiknock agents (ethylene dibromide and/ or ethylene dichloride, etc.)corrective agents (phosphorus, arsenic and antimony compounds, etc.),dyes, solvents and/ or diluents are illustrative of the types ofadditives which can be co-present.

The following examples illustrate the compositions of this invention andthe methods by which they are prepared.

EXAMPLE 46 To 1000 gallons of a commercial gasoline having a gravity of590 API, an initial boiling point of 98 F. and a final boiling point of390 F. are added 3.18 grams per gallon of lead as tetraethyllead, 0.6theory (based on the lead) of bromine as ethylene dibromide, 1.0 theory(based on the lead) of chlorine as ethylene dichloride, 0.25 gram ofmanganese per gallon as methylcyclopentadienyl manganese tricarbonyl and0.0002 weight percent (based on the gasoline) of the product of Example12. The resultant fuel possesses enhanced stability characteristics.

EXAMPLE 47 With a gasoline having an initial boiling point of 93 F., afinal boiling point of 378 R, an API gravity of 56.2 and atetraethyllead content equivalent to 0.2 gram of lead per gallon areblended cyclopentadienyl nickel nitrosyl to a concentration of 0.05 gramof nickel per gallon and product 3B to a concentration of 0.005 weightpercent (based on the gasoline). The finished fuel so formed possessesimproved stability properties.

EXAMPLE 48 To a gasoline having an API gravity of 51.5 C., an initialboiling point of 91 F. and a final boiling point of 394 F. are blended6.4 grams of lead per gallon as tetrabutyllead, 2 grams of manganese pergallon as octylcyclopentadienyl manganese tricarbonyl and 0.0008 weightpercent (based on the gasoline) of the product of Example 2. Theresultant fuel possesses very good stability.

EXAMPLE 49 With a gasoline having an initial boiling point of 93 F. anda final boiling point of 410 F. are blended 2 grams of lead per gallonas tetraphenyllead, 6 grams of nickel as diethylcyclopentadienyl nickelnitrosyl, 1 theory (based on the lead) of bromine as ethylene dibromideand 0.01 weight percent (based on the gasoline) of the product ofExample 4. The finished fuel has very good storage stability.

This invention also extends to the use in the above compositions ofmanganese pentacarbonyl (i.e., dimanganese decacarbonyl) The products ofthis invention are also very effective antioxidants for high molecularweight unsaturated hydrocarbon polymers, such as polybutadiene, methylrubber, polybutene rubber, natural rubber, butyl rubber, GR$ rubber,GR-N rubber, piperylene rubber, dimethyl butadiene rubber and the like.Thus a preferred embodiment of the present invention is a rubbercontaining as an antioxidant therefor, a product of this invention asdefined above. Another part of this invention is the method ofpreserving rubber which comprises incorporating therein a product ofthis invention as defined above. The stabilizer is incorporated into therubber by milling, Banbury mixing, or similar processes, or isemulsified and the emulsions added to the rubber latex beforecoagulation. In the various embodiments of this invention the stabilizeris used in small amounts, generally ranging from about 0.01 to about 5.0percent, based on the rubber.

As used in the description and claims, the term rubber is employed in ageneric sense to define a high molecular weight plastic material whichpossesses high extensibility under load coupled with the property offorcibly retracting to approximately its original size and shape afterthe load is removed. It is preferable that the rubber be asulfur-vulcanizable rubber, such as India rubber, reclaimed rubber,balata, gutta-percha, rubbery conjugated diene polymers and copolymersexemplified by the butadienestyrene (GRfi'S) and butadiene-acrylonitrile(GR-N or Paracril) rubbers and the like, although the invention isapplicable to the stabilization of any rubber, high molecular weightorganic material which is normally susceptible to deterioration in thepresence of oxygen, air, or ozone. The nature of these rubbers is wellknown to those skilled in the art.

Among the definite advantages provided by this invention is that thepresent rubber compositions possess unusually great resistance againstoxidative deterioration. Moreover, these compositions exhibit excellentnonstaining and non-discoloration characteristics. Furthermore, thenovel stabilizer is relatively inexpensive and easily prepared, andpossesses the highly beneficial property of low volatility. As is wellknown, a highly desirable feature of a rubber antioxidant is that ithave a low volatility so that it remains admixed with the rubber duringvulcanization and related process steps.

The rubber compositions of the present invention are illustrated by thefollowing specific examples wherein all parts and percentages are byweight.

EXAMPLE 50 To illustrate the enhanced oxygen resistance of the rubbercompositions of this invention and their excellent non-staining andnon-discoloration characteristics, a lightcolored stock is selected fortest. This stock has the following composition:

Pale crepe rubber 100.00

Zinc oxide filler 50.00 Titanium dioxide 25.00 Stearic acid 2.00Ultramarine blue 0.12 Sulfur 3.00 ls iercaptobenzothiazole 1.00

To the above base formula is added one part by weight of product 6-B andindividual samples are cured for 20, 30, 45 and 60 minutes at 274 C.using perfectly clean molds with no mold lubricant. Another set ofsamples of the same base formula which do not contain an antioxidant arecured 'under the same conditions.

EXAMPLE 51 To a synthetic rubber master batch comprising parts of GRSrubber having an average molecular weight of 60,000, 50 parts of mixedzinc propionate-stearate, 50 parts of carbon black, 5 parts of road tar,2 parts of sulfur and 1.5 pants of mercaptobenzothiazole is incorporated1.5 parts of the product of Example 8. This batch is then cured for 60minutes at 45 psi. of steam pressure.

EXAMPLE 52 Natural rubber stock is compounded according to the followingformula:

EXAMPLE 5 3 A butadiene-acrylonitrile copolymer is produced frombutadiene-l,3 and 32 percent of acrylonitnile. Two percent (based on thedry weight of the copolymer) of the product of Example 10, is added as'an emulsion in sodium oleate solution to the latex obtained fromemulsion copolymerization of the monomers. The latex is coagulated witha pure grade of aluminum sulfate and the coagulum, after washing, isdried for 20 hours at 70 C.

Each of the above illustrated rubber compositions of this inventionpossesses greatly improved resistance against oxidative deterioration ascompared with the corresponding rubber compositions which are devoid ofan antioxidant. Moreover, the flight-colored stocks of the aboveexamples exhibit virtually no discoloration or staining characteristicseven when subjected to severe weathering conditions and the like. Themethods of formulating the improved rubber compositions of thisinvention will now be clearly apparent to those skilled in the art.

The amount of stabilizer employed in the rubber compositions of thisinvention varies from about 0.001 to about percent by weight based onthe weight of the rubber. The amount used depends somewhat upon thenature of the rubber being protected and the conditions of service to beencountered. Thus, in the stabilization of natural and synthetic rubberto be used in the manufacture of tires which are normally subjected toexposure to the elements, as well as the action of sunlight, frictionalheat, stress and the like, the use of relatively high concentrations ofthis inhibitor is advantageous. On the other hand, when the article ofmanufacture is not to be subjected to such severe conditions, relativelylow concentrations can be successfully utilized. Generally speaking,amounts ranging (from about 0.25 to about 2 percent by weight giveuniformly satisfactory results.

Other rubbers and elastomers which can be prepared according to thisinvention are the rubbery poly'merizates of isoprene, butadiene-1,3piperylene; also the rubbery copolymer of conjugated dienes with one ormore polymerizable monoolefinic compounds which have the capability offorming rubbery copolymers with butadiene-1,3, outstanding examples ofsuch monoolefinic compounds being those having the group CH =Cexemplified by styrene. Examples of such monoolefinics are styrene,vinyl naphthalene, alpha methyl styrene, p -chlorostyrene,dichlorostyrene, acrylic acid, methyl acrylate, methyl methacrylate,methacrylonitrile, methacrylamide, methyl vinyl ether, methyl vinylketone, vinylidine chloride, vinyl oarbazole, vinyl pyridines, alkylsubstituted vinyl pyridines, etc. In fact, excellent stabilization isachieved by incorporating a product of this invention in any of the wellknown elastomers which are normally susceptible to deterioration in thepresence of air, such as elastoprenes, elastolenes, elastothiomers, andelastoplastics.

I claim:

1. As a composition of matter a reddish-yellow polynuclear phenolicmaterial containing 2 to 5 phenolic nuclei wherein each phenolic nucleusis mono-ortho-alkyla-ted and contains one hydroxyl radical and one alkylgroup of 3-8 carbon atoms ortho to said hydroxyl radical, said phenolicnuclei being linked together in a straight chain, each of said nucleibeing linked to the adjacent nuclei through 1-6 sulfur atoms in sulphidellinkages, said linkages being between carbon atoms of said nucleiselected from those carbon atoms ortho and para to said hydroxyl group,at least one of the terminal nuclei of said chain containing a chlorineatom, said phenolic material containing about 50 to 62 percent carbon,about 4.5 to 7.2 percent hydrogen, about 34 to 11 percent sulfur, andabout 16 to 5 percent chlorine, said phenolic material having an averagemolecular weight of about 500 to 740, and said phenolic material beingsoluble in hydrocarbon mineral oil.

2. As a composition of matter a substantially involatile, reddish-yellowpolynuclear phenolic material containing 2 to 5 phenolic nuclei whereineach phenolic nucleus is mono-ortho-alkylated and contains one hydroxylradical and an alpha-branched alkyl group of 3 8 carbon atoms ortho tosaid hydroxyl radical, said phenolic nuclei being linked together in astraight chain, each of said nuclei being linked to the adjacent nucleithrough 1-6 22 sulfur atonis in sulphide linkages, said linkages beingbe tween carbon atoms of said nuclei selected from those carbon atomsortho and para to said hydroxyl group, at least one of the terminalnuclei of said chain containing a chlorine atom, said phenolic materialcontaining about 50 to 62 percent carbon, about 4.5 to 7.2 percenthydrogen, about 34 to 11 percent sulfur, and about 16 to 5 percentchlorine, said phenolic material having an average molecular Weight ofabout 500 to 740, and said phenolic material being soluble inhydrocarbon mineral oil.

3. As a composition of matter a substantially involatile, reddish-yellowpolynuclear phenolic material containing 2 to 5 phenolic nuclei whereineach phenolic nucleus is mono-ortho-alkylated and contains one hydroxylradical and one tertiary butyl group ortho to said hydroxyl radical,said phenolic nuclei being linked together in a straight chain, each ofsaid nuclei being linked to the adjacent nuclei through 1-6 sulfur atomsin sulphide linkages, said linkages being between carbon atoms of saidnuclei selected from positions ortho and para to said hydroxyl group, atleast one of the terminal nuclei of said chain containing a chlorineatom, said phenolic material containing 52 to 54 percent carbon, 5 to5.5 percent hydrogen, 24 to 12 percent sulfur and 14 to 6 percentchlorine, said phenolic material having a molecular weight of 540 to590, and said phenolic material being soluble in hydrocarbon mineraloil.

4. Process of preparing a sulfur and chlorine-containing phenolicmaterial which comprises reacting (l) a mono-ortho-alkylated phenoliccompound having, ortho to the phenolic hydroxyl group, an alkyl group offrom 1-12 carbon atoms and (2) sulfur dichloride; conducting saidreaction at a temperature and for such a time that at least one terminalnucleus of said phenolic material is substantially chlorinated and saidphenolic material contains from 5-16 percent chlorine; there being atleast about 1.0 mole of said sulfur dichloride per mole of phenoliccompound as reactants.

5. Process of claim 4 wherein said reaction is partially conducted at atemperature of 4045 C., said temperature is allowed to rise to 60'65 C.and then the remainder of said reaction is conducted at 60-65 C.

6. Process of claim 4 wherein said phenolic compound and said sulfurdichloride are reacted at a temperature of from between 0 and C.

7. Process of claim 6 wherein said alkyl group is alphabranched and hasfrom 3-12 carbon atoms.

8. Process of claim 7 wherein said alkyl group is tertiary butyl.

9. Process of claim 8 wherein there is from about 1.1 to about 1.5 molesof sulfur dichloride per mole of phenolic compound.

10. Process of claim 9 wherein there is about 1.5 moles of sulfurdichloride per mole of phenolic compound.

11. Process of claim 10 wherein said reaction is partially conducted ata temperature of 40-45 C., said temperature is allowed to rise to 60-65C. and then the remainder of said reaction is conducted at 60-65 C.

References Cited in the file of this patent UNITED STATES PATENTS2,239,534 Mikeska et a1. Apr. 22, 1941 2,362,293 McNab et a1. Nov. 7,1944 2,409,687 Rogers et al. Oct. 22, 1946 2,569,122 Adelson Sept. 25,1951 2,621,172 Teeter Dec. 9, 1952 2,767,163 Peters Oct. 16, 19562,812,307 Saives Nov. 5, 1957

1. AS A COMPOSITION OF MATTER A REDDISH-YELLOW POLYNUCLEAR PHENOLICMATERIAL CONTAINING 2 TO 5 PHENOLIC NUCLEI WHEREIN EACH PHENOLIC NUCLEUSIS MONO-ORTHO-ALKYLATED AND CONTAINS ONE HYDROXYL RADICAL AND ONE ALKYLGROUP OF 3-8 CARBON ATOMS ORTHO TO SAID HYDROXYL RADICAL, SAID PHENOLICNUCLEI BEING LINKED TO THE ADJACENT NUCLEI THROUGH 1-6 SULFUR ATOMS INSULPHIDE LINKAGES, SAID LINKAGES BEING BETWEEN CARBON ATOMS OF SAIDNUCLEI SELECTED FROM THOSE CARBON ATOMS ORTHO AND PARA TO SAID HYDROXYLGROUP, AT LEAST ONE OF THE TERMINAL NUCLEI OF SAID CHAIN CONTAINING ACHLORINE ATOM, SAID PHENOLIIC MATERIAL CONTAINING ABOUT 50 TO 62 PERCENTCARBON, ABOUT 4.5 TO 7.2 PERCENT HYDROGEN, ABOUT 34 TO 11 PERCENTSULFUR, AND ABOUT 16 TO 5 PERCENT CHLORINE, SAID PHENOLIC MATERIALHAVING AN AVERAGE MOLECULAR WEIGHT OF ABOUT 500 TO 740, AND SAIDPHENOLIC MATERIAL BEING SOLUBLE IN HYDROCARBON MINERAL OIL.
 4. PROCESSOF PREPARING A SULFUR AND CHLORINE-CONTAINING PHENOLIC MATERIAL WHICHCOMPRISES REACTING (1) A MONO-ORTHO-ALKYLATED PHENOLIC COMPOUND HAVING,ORTHO TO THE PHENOLIC HYDROXYL GROUP, AN ALKYL GROUP OF FROM 1-12 CARBONATOMS AND (2) SULFUR DICHLORIDE; CONDUCTING SAID REACTION AT ATEMPERATURE AND FOR SUCH A TIME THAT AT LEAST ONE TERMINAL NUCLEUS OFSAID PHENOLIC MATERIAL IS SUBSTANTIALLY CHLORINATED AND SAID PHENOLICMATERIAL CONTAINS FROM 5-16 PERCENT CHLORINE; THERE BEING AT LEAST ABOUT1.0 MOLE OF SAID SULFUR DICHLORIDE PER MOLE OF PHENOLIC COMPOUND ASREACTANTS.